Composition and process of manufacturing the same.



J. AYLSW ORTH. COMPOSITION AND PROCESS OF MA NUFAGTURING THE SAME.

APPLICATION TILED MAY 14, 1909.

Patented July 7, 19%

Q? La toz- Smog,

JONAS W. AYLSWORTH, OF EAST ORANGE, MESNE ASSIGNMENTS, T0 CONDENSITE NEWJERSEY, ASSIGNOR, in: DIRECT AND COMPANY. or. AMERIGA, or EAST omen,

NEW JERSEY, CORPORATION OF-NEW. JERSEYk COMBOSITION' AND PROCESSOF'MANUFAUTURING THE SAME nioaeeo.

Specification of Letters Yatent.

Patented Jam, 1914;,

1 Application filedMayM, 1909. Serial novice-p603 To all whom it mayconcern:

Be it known that I, J oNAsW. AYLSWORTH, a citizen of the United States,and a.-resi-' dent of East Orange, in the county of Essex and State ofNew Jersey, have invented a certain new and useful Composition andProcess for Manufacturing the Same, .of wliifh the following is adescription:-

Y molding various articles, such: as may be made from celluloid, hardrubber and kindred substances, and also, to the production of'syntheticresins, which may be used for varnish gums, forbaking enamels andjapans, and as solid solvents for pyroxylin and cellulose acetate andthe like. The composition first mentioned may likewise be used for theformation of insulators, phonograph records, and in many otherconneotions.

My invention comprises more specifically first, the formation of a hardfusible pheno resin from phenol or cresol by condensation withformaldehyde, the same being. claimed as a new product and a process formanufacturing the same being also claimed. This is the synthetic resinabove referred to. Secondly, my invent on comprises the formation of anultimate infusiblecondensation product of a phenol and formaldehyde,- orequivalents of these substances, this infusible product being very hardand chemically inert, but, when made in'the preferred mannersufliciently plastic on application of heat, as hereinafter described,to be shaped or pressed into 'form' at suitable temperatures. Thisultimate condensation roduct is preferably formed from the iienoliresin, referred: to aboveybut an i sible condensation product havingmany of the advantages of this preferred product may-beformed'bytreating various of the shellac substitutes or phenol resins now known,in-a manner to be later described. The ultimatecondensa-w tion productreferred to may be formed di;

rectly in the molds-in the desiretil dinal'shape,'v

or it may be cast intosolidvslabs, bars, cyl l inders, or other desired.form, and subse-I uently heated and pressed into the desineda The degreeof plasticity; will rvaryv' iIltaCCOtdanCe :with .variousfoflthez'i 1edin ents of the'mass. This ultimate con ensa-- invention relates tocompositions for tion product, according to difl'enent phases of myinvention,ma be either a hard, infusible phenolic con ensation productorit may be asolid solution of'i'fich aflcondensation product and asolid solvent or plasticity ingredient, of a nature to be described.This latter product, which is the one'referred to above as sufiicientlyplastic, on application fofheat to be shaped or pressed to form atsuitable tem eratures, is not claimed herethe same, orms the subjectmatter of my application Ser. No. 630,894, filed June 2, 1911, which isa division of this application. Also, a product and process, in whichthe solid solvent element referred to consists specifically of-anorganic acid or anhydrid thereof, are described and claimed in myapplication {Ser. No.- 630,893,-filed June 2, 1911, which, as to suchfeatures, constitutes a division of this application. Herein I willclaimultimate condensation products, made according to my invention, andprocesses for making such products, which products and processes do notinvolve the use of the solid solventelements described herein.

The objects of'my invention are accordingly the production of the hardfusible phenol resin, and the infusible flensationi products, referredto, together with the novel processes bywhich the same are produced orwhich contribute to the production of the sar'ne, all as hereinafterdescribed and claimed.

In order that my invention-may be more clearlyunderstood, attention ishereb diing part of this specification, and illustratereinafter desoribed;

in, but, toLget er'with a process for making ing diagrammatically oneform of appara-,

ultimate conrected to-the accompanying drawing, ormfibei .'-produced insev-' of the ultimate resin, and dissolved therein.

tages of my invention, formaldehyde, preferably in polymerized form, isincorporated with the phenol resin, in the proportion of about 5 to 7%per cent. of the Weight of the Thesolid polymerized forms offormaldehyde are preferred because they are the only anhydrous formsinwhich formaldehyde occurs. Phe- I101 resin is non-Water-soluble, andconsequently will not mix with a water solution of formaldehyde, but isa solvent when in melted or dissolved condition for anhydrousformaldehyde. If formaldehyde solution is used instead of polymerizedformaldehyde,

heating to ,-reaction temperature drives ofl the water and aconsiderable part of the formaldehyde from the solution, and convertsthe remainder of the formaldehyde into the polymerized form, which thendissolves in .and reacts with the resin. With I this method it is moredifficult to obtain the correct reacting proportion of the formaldehydecomponent. Also, preferably, a small percentage of a water-combiningelement, such as an anhydrid of an organic acid, and a percentage of asolventof the final product, which may also act .as athinning or antiviscosity agent, are incorporated therewith, the species of my inventionin which the final product solvent i's-used, however, not, being claimedherein, as stated above. The nature and purpose of the water-com-.bining element and the final product solvent element will be describedhereinafter.

Having obtained theabove mixture the same b may be cast in suitablemolds for the formation of the desired articles or for the formation ofrods, sheets, tubes, or slabs, ,or the like,.from which the desiredarticles may subsequently be made by heat and pressure, or by forming bytools. The molds and their contents are heated sufiiciently to transformthe product .into a hard, infusible,

chemically inert substance, the temperature resin before mixing, thecharacter of the to which the same is heated in practice varying between260 and 400 Fahrenheit, depending on the treatment of the phenolwater-combining element and the character of; the molded article. Theheating may be accomplished by casting in suitable .steamjacketed molds,or by placing the molds and contents in suitable ovens for a timesuflicient .to allow the mixture to interact and" harden. This time mayvary within Wide limits, depending on the thickness of the article andthe character of the mass. Thin sheets and small articles may behardened in a few minutes, while larger masses and objects of specialcharacter may require gradual heat' to,the lowest temperature necessaryfor t e reaction to take place and continued heating at suchtemperature, or

at an elevated temperature, for severalhours. The ultimate product soformed will not melt atany temperature below that of its decomposition,but will soften and become sufliciently plastic at from 240 to 300 F1,to be further shaped by pressing in suitable dies or molds, when madewith a final product solvent element, as stated. The product also isinsoluble in common solyents, regardless of the incorporation there- 'mor omission therefrom of the final product solvent elements referred to.The degree of plasticity maybe controlled to a certain extent bythenature of the solvent ingredient and proportions thereof, and byvarying the proportions of the polymerized fprmaldehyde, added to'thephenol resin. In case the plasticity is controlled by varying theproportion of the polymerized formaldehyde, the phenol resin itself'actsas a solvent for the ultimate product to an 'ex tent suflicient torender it plastic when heated, in this case the proportipn .offormaldehyde-being less than in products in which the plasticity iscontrolled by added solvent elements.

As stated,- the phenol resin or fusible condensation product may beformed in several different ways. With the first of these methods, thephenol or cresol .is heated'in a autoclave to a temperature of from 260to 340 F., and maintained at such temperature. I prefer to use atemperature between 280 and 300 F., but a higher temperature isnecessary under some circumstances. The

into a multitude of bubbles, which pass upward through the phenol andare absorbed therein and combined therewith. A. presof the contents ofthe autoclave is maintained in the autoclave by means of feedingcompressed formaldehyde gas therein as Formaldehyde sure in slightexcess of the vapor tension rapidly as it combines with the phenol. At

a pressure of 50 to 100 pounds per square inch, good results may beobtained. The

reaction may be carried on more rapidly athigher temperatures than thosewhich I have above described as preferable and conven- I ient. Thepressure used is aboutthe' same as that of water vaporat the temperatureused. I

. The contents of the vessel are preferably kept in rapid circulation bya propeller or steam when necessary,

'for carrying oflz' the excess heat above the 'tially heated. Such aheat in excess ofabout 240 F. and cast in ingots for subseand theformaldehyde in the form of an "under no counteracting cause "of thesubsequent treatment other convenient means. The reaction proceedsrapidly and provision should be made proper reaction tem erature, whichis the temperature to whic the phenol. was ini-g that necessary tomaintain the reaction term 1 perature will be generated by the reaction:itself. The supply of formaldehyde is com. tinned until. a samplewithdrawn for test, shows only a very small percenta e of free orunchanged phenol.

opened for the escape of steam, which is regulated by' a suitable valve.The contents. of the chamber are then heated tocomplete dehydration,which requires about 400 F. of heat. The contents are then cooled toquent use, or passed into suitable mixing vessels for immediate use.

Referring to the drawin illustrating a means for practising the rstmethod of forming 'phenol resin described, formaldehyde is generated inthe generator 1, and passes through condenser 2, which removes unchangedmethyl-alcohol therefrom, to the gasometer 3,, which is provided with anoil seal and is adapted to be steam heated. Formaldehyde' gas istakenl-t-herefrom as desired, by pump 4 and allowed to pass asbubblesfrom perforated pipe 5 into'the liquid phenol 6 in. the autoclave7 which is provided with steam jacket 8, agitator 9, pressure gageld,vent 11 for the escape of which is regulated by a valve 11, and safetyvalve 12. Provision should be made for steam'heatin the pipes throughwhich i the formalde yde passes, and for passing cooling water throughsteam jacket 8 when the reaction has. started to prevent the temperaturefrom rising abovethe proper reaction temperature'. This can be regulatedby thermometer 13.

In the second of the methods above referred to by which-the phenol resinmay he formed, phenol and a 40 per cent. solution of formaldehyde,together with a small percentage of either an acid or a basicacceleration or catalytic agent, are treated and allowed to interacttoform rapidly the ultimate condensation product of the phenol infusibleporous mass, This mass will, be porous because of the evolution of thedissociation gases, which as is well: known, takes place when thereaction between; the phenol and formaldehyde is allowed to rapidlyensue at an elevated temperature and ressure. In this case, however,this is o no moment, he-

of'the The supp y of gas is then stopped and a vent in the autoclaveismass. This infusible mass is preferably crushed and pulverized and thenbaked at approximately 350 F.,- whereby entrapped water and acid vaporsare expelled. The powdered and dried substance is mixed with phenol orcresol in approximately the proportion of two parts of the finalcondensation product to one part of the phenol, and heated in a closedvessel under its own pressure to" a temperature of from 450 to 550 F,for several hours.

the ingredients of the mass go into the so- By this treatment lutionwith alchemical change, whereby the product reverts or is broken down tothe uslble resin, presumably by reduction of the formaldehyde element inthe combination. By this means after the distillation of the excess.unchanged phenol, a resin is formed similar to that described in theprocess first described.

The ultimate condensation product after solution in the phenol, asstated in the last described process, may be entirely converted into thephenol resin by means of the first process, that is to say, after thesolution of the porous ultimate condensation product in the phenol orother solvent used,

com ressed formaldehyde gas may be forced into the solutionas fast as itcombines with the excess phenol, and the process carried on irom thatpoint as described in the first process. In this process, however, therewould be no distillation of excess phenol, as was the case in the secondprocess, the excess phenol being combined With the added formaldehyde asjust stated, to form more phenolresin. Acid or basic condensing agentsasabove noted, are apparently necessary in small percenta s in thisprocess of breaking down a p enol 'infusible condensation product to thefusible condensation product or phenol resin, as material so formedwithout such agents does-not readily dissolve in the phenol-except atmuch highertemperature.

It Is especially a'dvanta one to combine 'methods 1 and 2, as justescribed, because thereby a manufacturer is enabled to use scrapmaterial and discarded and. imperfect articles. Phenol and 'cresol arethe preferred solvents for the ultimate condensation product, but othersolvents may be used, such as a mixture of phenol and naphthalene, thenaphthalene in this case being removed by distillation after thesolution is formed. I

The phenol resin-obtained by any of the methods-described after completedehydrationand removal of excess phenol is a hard resin, very similar intexture to copal and kauri guns", It is soluble mall proportions inalcohol, acetone and other of the common solvents from which it tremainsunchanged after evaporation of the solvents. n

It is fusible and practically unchanged when heated to 420 F. It melts.at about 220 F., but has no sharp melting point passing through variousdegrees of. viscosity, untilat 250 F. it may readily be'poured and at350 F. it becomes quite thinly fluid. It

acts as a weak acid-toward bases with which it combines. It is solublein shellac, resin and similar substances when fused therewith. Thisresin will not form the hard infusible condensation product described bySmith, Story, Baekeland, and others, (see English Patents 16,247, of1899, to Smith, and 8,875

of 1905, to Story, U. S. Patents, 982,699 to dehy'de solutions are-givenas volume dehy aldehydes in general, other than those mentioned, and ifthe percentage of formaldehyde or its polymers exceed about 7-} percent., the excess escapes as bubbles in the mass and renders the latteruseless for some purposes.

In additionto methods 1 and 2 and the combination thereof previouslydescribed for forming phenol. resin, I may use a so- I lution offormaldehyde in the proportion of 1000 arts of phenol to 750 parts offormaldb by weight, and heat the mass to a temperature'of from 3.00degrees to 320 degrees F. under its own pressure, without any agent. Ifa' 40% solution of formaldehyde is used, the proportions should be about650 parts of formaldehyde to'1000 parts of phenol. In the aboveproportions, formalercentages. The weight percentage. of theformaldehyde in the solution is: appr JXIlmately 5% less. Theproportions of formaldehyde -solution given in the formulae are slightlymore than the required. amount to allow for: losses during the process.In this method as in method No.1 above described, care must be takentoavoid the presence of any impuritywhich will actas an accelerator or'catalytidagent," otherwise diflicu'ltly fusiblev and vjery viscidproducts will result. For instance, if the-operation is carried out .inan' iron-vessel, carl-niustbe taken to have the iron well enamledf orlined with a metal which will not modify the product." Iron and lead somodify the product as to render the latte'runfit. Tin,

or tinned copper, or nickel, are metals which can be used to line thevessel without modifying the product. If crude phenol. .or

cresol are used, they should first be refined by distillationgtoeliminate basic metallic impurities as well as mineral acids. In processNo. 2, above described, for making phenol resin, when naphthalene andphenol are used as a solvent, for the ultimate condensation product tobe transformed or broken down into the phenol resin the phenol must beadded in the proportion of about 20 per cent., of the condensationproduct and the naphthalene in about the proportion of from 50 to'100per cent. of the condensation product. I

In the formation of the ultimate condensation product, the phenol resinis mixed as stated, with formaldehyde which is preferably polymerized.The substances ofthis character which I consider best adapted for thepurpose are trioxymethylene and dioxymethylene, in an amount which issuflicient to combine with nearly all the resin, so that there may be noexcess of formaldehyde or' polymer thereof to cause bubbling of the massduring the hardening operation. Such anamount may vary between 5 and 7per cent. of the weight of phenol resin used.

Formaldehyde, not polymerized, may be used in place of the polymerizedsubstance,

in which case the-polymerized formaldehyde w ,is formed by evaporationduringthe rocess. It is usually impracticable to make the phenol resinentirely free from uncombined phenol, and the small variable percentageof phenol makes it necessary in the formation of the mixture for theultimate product to vary the percentage of paraformaldehyde,'which maybe either di-oxymethylene or tri-oxymethylene, or amixture of the two,in the mixture with the resin, in accordance with the percentage offree-phenol,

ascertained by test. The phenol combines with a much greater proportionof polymresin. By varying the percentage of the '105 erized formaldehydethan does the phenol polymerized formaldehyde as indicated, the freephenol in the phenol resin may all be taken into combination. Theproduct thus obtained after heating the phenol resin and the otherelementsmentioned in properproportions .to a temperature of from 280 to-400 F. or higher, is somewhat similar to the final condensation productdescribed by Baekeland and others, but differs in four importantparticulars, as follows First, the ingredients of the ultimate productmay be Baked during-the hardening operation by heating as hereinafterexplained to a temperature of from260-to 350 F. without becoming porousfrom gas bubbles other than such as may be entrapped by the mass whencast, thus rendering it unnecessary to heat or perform the hardeningoperation under a counteracting pressure in closed vessels.

Secondly, theultimate condensation product so formed, softenssufiiciently to-allow further shaping, as stated, at 'a temperaturebetween 240 and 300 F.,whi1e at the same time it is infusible at anytemperature lower than that of its decomposition. Thirdly, my product istougher and less brittle in -texture than the substances previously arenaphthalene and some of its derivatives, I

known in the art, as referred to above, because no basic accelerating orcatalytic agent isnecessary or even desirable. This distinction,however, applies only to the product made with phenol resin formed inaccord ance with method No. 1 described above, since in method No. 2, acondensing agent is necessary. This absence of a condensing agent orother impurity permits the formation of an ultimate product which isalmost colorless, when desired. Fourth, the ultimate product heredescribed and claimed may be made of exact and definite ultimatecomposition under perfect control, whereas, by the known methods invogue, an intermediate and final product are made which are not undersuch control, resultingin excessive losses. Economy in manufacture ofthe ropluct is also enhanced. The ultimate pro act is furtherdistinguished from the similar substances heretofore known by theincorporation therewith of a water-combining element, and a finalproduct solvent ele ment in varying percentages.

The, water-combining element takes care of traces of water which may beexpelled during the baking operation. This results in a clearer and moretransparent product, although I do not regard the inclusion of thiselement as'absolutely essenti'aL- Examples of this class are benzoicanhydrid, phthalic anhydrid, and any such organic anhydridsas aresoluble in and miscible with the mass, and are not decomposed attemperatures used. The final product solvent element contributes greatertoughness to the product by counteracting the brittle nature of thefinal product and renders the ultimate mass plastic whenheated, thusrelieving internal stresses during the baking and hardening operationsand subsequent cooling.

133 final product solvents, I include only substances which willdissolve the ultimate condensation product or combine therewithat thebaking temperature, render it-plasti'c at such temperature, and remainas a part of the roduct in the condition. of .Tsolid -s01uetio'n.xamples of substances of this class such as. nitro and chloro.derivatives, .espe cially the mono-intro and di-n-itro naphthalenes,di-nitro benzene, preferably the meta variety, aeetanilid, ri ci-noleicacid, and. ricinel'aidic acid, and-their anhydrids'; benfzoie acid andanhydrid, and di-phenylaminv naphthalene which is noted among the finalproduct solvents is a, substance which tends to'volatilizesliowly atordinary temperatures whenialone. It does not, however, volatilize fatordinary temperatures when dlu-tion with the ultimate condensationproduct, and within the proportions given in some of the followingexamples. The naphthalene derivatives mentioned when in solid solutionwith the ultimate condensation product do not volatilize either atordinary or atelevated temperatures. In many cases anhydrids of organicacids may be added which will perform both the water absorbing functionand the solvent or plasticity function. Such substances include benzoicanhydrid and ricinelaidic anhydrid. For special uses, I may'alsoadvantageously add small percentages of acid catalytic or condensingagents when mixing the phenol resin and the other ingredients for thepurpose of causing the final reaction to, ensue more rapidly and at alower temperature. Effective agents for this purpose are small amountsto 2 per cent.) of the hydrochloride of a variety of organic radicals,such as anilin hydrochlorid, hydroxylamin hydrochlorid, andpinene-hydrochlorid. By the use of such agents the hardening reactioncan be made to take place at tempera tures much below 250 F.; withoutsuch agents the reaction proceeds much IIllOI'G slowly and at highertemperatures. Such a composition is particularly well suited for hardvarnish and lacquers by mixing and dissolving in alcohol, 'or equivalentvolatile solvents, and when-dried heating moderately in a steam oven.Suitable chemically inert pigments andffillers may be incorporatedsired, be given any desired color by the addition of suitable pigments.Chemically inert cheaper substances in powdered or fibrous form may beincorporated with the ;mass before bakingi in widely varying .per

cents.,"when desire Preferred formulae for'masses which are to behardened in molds without subsequent Paradormaldolryde pressingoperations are as ifollOwsz- I For light colored and transparentproducts.

' Parts by weight. (1 Phenol resin 100 Polymerized torma'ldehyde 5 to 7Beuzoic anhydrid 5 to .10 (2) Phenol resin... 100 ht due 51:0 10 PffimerlzedjorMldehyde. to 7 (3) Phenol 100 Benzoicanhydrl to 4 Naphthaleneto 10 Tri-oxymethylene. to 8 mama-cam products. i Parts by(4.)?11enolresin Meta di-nltro'benzene.

6O .plastic compositions indicated in the formu:

- be as follows:

y weight. g fifigd ,1,2 spec lge gravity 1.257

enzoican y 1 Para-formaldehyde... 9 i gfi gzggfi I S ecificgravity1.248.Phenol resin 100 Para-formaldehydo.. 6 l g gggfi 1 Specific gravity LMG.Phenol resin 100 Phenylacetamid (acetanilid) 13 @3 fif fig;Para-formaldehyde 8 pang; I Phenol resin 100 Specific gravity 1.324.'letra-chloro naphthalene. 20, Opalesccnt a m b e r Para-formaldehyde. 8color. Phenol resin 100 Specific gravity 1.317. Di-nitro benzene (meta)Deep red wine color. Benzoic anhydrid 2 transparent a n dPara-formaldehyde 6 clear.

For non-melting plastic compositions.

(5) Phenol resin Naphthalene Para-formaldehydc.. 5 to 20 (6) Phenolrosin 100 -Naphthalenc...... 10 to 20 Benzoic anhydrid. 1 to 5larmformaldehyde 5 to 10 (7) lhenol resin 100 Meta di-nitro benzene 10to 50 Para-formaldehyde 5 to 7 (8) lhenol resin 100 Di-nitro benzene...10 to 40 B enzoic anhydrid.. 1 to 5 Para-formaldehyde 5 to 8 (9) Phenolresin...;- 100 'Acetanilid 7t0 30 Para-formaldehyde 6 to 8 (10) Phenolresin....; 100 'letra chloro naphthalene 10 to 25 Bcnzoic anhydrid 1 to5 Para-formaldehyde. 5 to 8 (l1) Phenol resin 100 Mono-ni rous.hthalene. 7 to 30 Para-formalde yde 6 t0 8 Benzoic anhydrid 1 to 5 Thespecific gravit-ies and other qualities of various of these compositionswhich are given merely as examples, were found to Parts The specificgravity of the phenol resin used was found to be 1.240. This substanceultimate condensation product, the ingredi-- ents are mixed and freedfrom air bubbles by standing in molten condition or by vacuum treatmentor' by centrifugal treatment attemppratures below 250 F. or freed fromair bu bles in any other suitable manner. The mass is then poured intomolds and is preferably slowly heated to a temperature of from 260 to270 F., at'whichtempera- 50 ture it is maintained for a sufficienttimeto render the mass infusi-ble, and subsequently is heated for a shorttime to a temperature of 300- to 350 F. The ingredients may also beheated to from 320 to 350 F. under counteracting pressure, as is done intheart of vulcanizing rubber. When no counter-.

acting pressure 1s used, from one-half to four hours is required beforethe final temperav ture may be reached, this time varying with thethickness of the object molded. The

he 5 to 11 become sufiiciently plastic to mold at from240 to 300 F.

It will be seen that a condensation product, which is fusible andsoluble in common solvents, is formed by the reaction of-a phenol andformaldehyde in such proportions that the phenol is almost entirelycom-.

bined with the formaldehyde, and there is no excess or freeformaldehyde.When formaldehyde is added to the resinized phenol'or phenol-resin soproduced and the mass is heated to a temperature suitable for thereaction, an infusible hard ultimate condensation product is formedwhich is chemically inert, insoluble in common solvents, and the otherproperties previously noted.. My invention accomplishes the productionof a synthetic resin, such as the phenol'resin above referred to, and anultimate condensation product, such as that described, having no excessof formaldehyde. As far as I am aware, no one prior'to my invention, hastaken advantage of these facts, 4

to control the production of the desired sub-' stances, or has clearlyrecognized the existence of such facts. Furthermore, no one within myknowledge has recognized the possibility of forming an ultimatecondensation product, such as described, dissolving the same in a properamount of phenol or other solvent and breaking down, the 111th mateproduct to a fusible condensation product, which is lowered in theproportion of its formaldehyde element, or practised the said processfor the production of a fusible resinized, phenol. The action of anultimate phenol condensation product in the presence of phenol in themanner referred to would seem to confirm the belief that the hardeningof the ultimate condensation product and the achievement of the otherproperties noted, are due to the combination of a further amount offormaldehyde with the phenol resin after the phenol element thereof hasbeen completely satisfied by combination with formaldehyde in theformation of the lower condensation product or phenol resin. In the.case of the breaking down process by which the ultimate product isreduced to the fusible condensation product, the formaldehyde combinedwith the phenol resin is apparently taken out of combination with. thephenol resin by the excess phenol with which it combines to formmorephenol resin, the excess of phenol above that necessary for suchcombination being distilled away, or converted into phenol resin byadding more formaldehyde. The shellac substitutes reviously referred toare substances wel known as a class, being synthetic resins, more orless fusible and soluble, which are intended to be used as substitutesfor natural resins, colophony, etc. the condensation of a phenol andformalde- They are usually formed byhyde, which are incorporatedtogether in di'fl'erent proportions in different products. The phenolresin made and described by .me belongs to this class, but has'thespecial characteristics described which render it especially usefulinthe preparation of my.

ultimate, infusible product. The phenol resin described is, as I have"stated, completely anhydrous when heated to about 400" F. for completedehydration. When latter as containing no water either in free orcombined state. The ultimate infusi ble product formed by the reactionbetween such an anhydrous phenol resin and an added amount of anhydrousformaldehyde or its polymers, as described, is also anhydrous, asstated, if the small amount of water evolved by the reaction between theresin and the added formaldehyde is permanently fixed by combinationwith a water-combining element, such as I have described. That is, if awater-combining ingredient is present in the mass, as stated, the waterevolved is combined with the wa.t-er-combining element, and ispermanently fixed to form a harmless ingredient in the mass. Thus, forexample,

, formed into a hard infusible chemically :inert product, substantiallyas described.

if phthalic or benzoic anhydrid is used as the water-combining element,as stated, the water evolved combines with the same to form f bleproduct consisting in determining the percentage of uncombinedphenol ina fusible phenol resin incorporating therewith a .quantity offormaldehydecompound hav-' 'ing the formula (CH OML where n is a thecorresponding acid, as stated.

. The term fusible appearing in the claims, as qualifying a p-roductsuchas. my.

phenol resin, denotes a, product. which melts and becomes liquid, whensuficiently heated, under atmospheric pressure.

The term infusible in .the claims, as

I qualifying my ultimate product, denotes a substance which does notflow or become liquid, when heated to any temperature, un-

When an ultider atmospheric pressure. mate product solvent element isadded, or an excess of phenol resin is used as a solvent for theultimate product as stated, the. mass becomes sufficiently plastic to bereadily pressed or molded to shape, but does not fuse.

The word phenol as employed in the claims is-intended to include theequivalents of phenol for the purposes of this invention, and the wordformaldehyde is intended generically to include the polymers and otherrecognized equivalents of formaldeh de.

It will be noted that my invention, comprisingthe incorporation offormaldehyde, preferably in polymerized, solid anhydrous form, asdi-oxy-methylene' or tri-oxy-methylene, with phenol resin, may be statedto consist in incorporating with phenol resin a be said to be frcefrombasic substances and mineral acids.

Having now describedmy 111Ve1'1t10l1, what I claim as new and desire .tosecure by Letters Patent, is as follows 1. The process of forming a hardinfusible product consisting in incorporating with a fusible phenolresin a formaldehyde compound having the formula (GI-1 0M where n is anumber less than 4, of a quantity just suflicient to combine withsubstantially all of the same, and heating the mass sufliciently tocause the reaction to ensue and the mass to be transformed into a hardinfusible chemically inert product, substantially as described.

2. The process of forming a hard infusible product consisting in formingan an- ;hydrous fusible phenol-formaldehyde COIlr densa-tion productcontaining no uncom-' Ibined formaldehyde, incorporating therewithaformaldehyde compound having the T formula ('CH O)n where n" is anumber less than 4, of a quantity just sufiicient to com- ;bine withsubstantially all of the same, and ,heating the mass sufficiently tocause the reaction to. ensue and the mass to be trans- 3. The process offorming a hard infusinumber less than 4, calculated to be in properproportion to cause the combination of the formaldehyde compound uponapplication of sufficient heat, with substantlally all ofthe resin anduncombined phenol contained therein to form the desired substance,

and heating. the mass to a temperature, and

for a length of time suflicient to cause a com-v plete hardenlngreaction between the said ingredients, said temperature not to exceed350 F, substantially as described.

4. The process of forming a hard infusible, insoluble product,consisting in incorporating with a fusible anhydrous phenol resin, ananhydrous formaldehyde compound having the formula (CH O-M where n is anumberless than 4, in an amount the .variation of which is determined bythe ascertained percentage of uncombined phenol in the 'resin to be asufficient amount to form a hard infusible, insoluble product, andapplying heat sufficient, to cause a condensation reaction between theresin and ble product. consisting in incorporating with a fusibleanhydrous phenol resin, a formaldehyde compound having the formula (CHO)n wheren is a number less than 4, in an amount determined bythepercentage of uncombined phenol in the resin to be the proper amountto entirely enter into combination with substantially all of the resin,and uncombined phenol contained therein, on application of suflicientheat, and applying heat sufiicient to cause a condensation reactionbetween the ingredients forming the desired hard infusible tially asdescribed.

6. The process of forming a hard infusible product consisting inincorporating with afusible phenolresin a solid anhydrous polymerizedformaldehyde just sufiicient amount to react with substantially all ofthe same, and heating the mass sufficiently to cause the reaction to'ensue and the mass to be transformed into a hard infusible chemicallyinert product, substantially as deproduct substan scribed.

7. The process of forming a hard infusible pro duct consisting informing a hard fusible phenol resin, completely dehydrating the same,incorporating therewith from 5 to 7 of an vanhydrous formaldehydecompound having the formula (CI-1 0))? Where n is a number less than 4,and heating the mass at a temperature of 260 F. or over, for asufficient time to transform the mass into an infusible chemically inertproduct substantially as described.

with the fusible-condensation product, with out any excess offormaldehyde compound, and heating the mass at a temperature, and

orming a comfor a time sufficient to transform the prodnot into a hardinfusible chemically inert substance, substantially as described.

9. Asa new composition of matter, a hard infusible condensation productof a fusible anhydrous phenol resin and an anhydrous formaldehydecompound having the formula (CH O)n where n is a number less than 4:,

. the said product being free from basic substances and mineral acids,substantially as described.

This specification signed and witnessed this 13th day of May 1909. 1

JONAS W. AYLSWORTH. Witnesses: I v DYER SMITH,

ANNA-7R. KLEHM.

